NZ287734A - Preparation of n-phosphonomethylamino carboxylic acids using dialkyl phosphite - Google Patents
Preparation of n-phosphonomethylamino carboxylic acids using dialkyl phosphiteInfo
- Publication number
- NZ287734A NZ287734A NZ287734A NZ28773495A NZ287734A NZ 287734 A NZ287734 A NZ 287734A NZ 287734 A NZ287734 A NZ 287734A NZ 28773495 A NZ28773495 A NZ 28773495A NZ 287734 A NZ287734 A NZ 287734A
- Authority
- NZ
- New Zealand
- Prior art keywords
- formaldehyde
- salts
- phosphite
- acid
- reaction
- Prior art date
Links
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 9
- 150000001735 carboxylic acids Chemical class 0.000 title description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 124
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 150000003839 salts Chemical class 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 239000011541 reaction mixture Substances 0.000 claims abstract description 23
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 8
- ZZLRWERPJLNCEZ-UHFFFAOYSA-N phosphonomethylcarbamic acid Chemical compound OC(=O)NCP(O)(O)=O ZZLRWERPJLNCEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 48
- 239000003054 catalyst Substances 0.000 claims description 39
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 238000006460 hydrolysis reaction Methods 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- SCQKIXZMVJQAMS-UHFFFAOYSA-N (2-hydroxyethylamino)methylphosphonic acid Chemical compound OCCNCP(O)(O)=O SCQKIXZMVJQAMS-UHFFFAOYSA-N 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- 230000007062 hydrolysis Effects 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 238000004679 31P NMR spectroscopy Methods 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical group COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- ANYPUYLKMDXVRK-UHFFFAOYSA-N 2-aminoethanol;formaldehyde Chemical compound O=C.NCCO ANYPUYLKMDXVRK-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 23
- 239000000243 solution Substances 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000007747 plating Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- NYQDCVLCJXRDSK-UHFFFAOYSA-N Bromofos Chemical compound COP(=S)(OC)OC1=CC(Cl)=C(Br)C=C1Cl NYQDCVLCJXRDSK-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 229910052793 cadmium Inorganic materials 0.000 description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229930040373 Paraformaldehyde Natural products 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229920002866 paraformaldehyde Polymers 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 5
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- -1 phosphite diester Chemical class 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000005562 Glyphosate Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229940097068 glyphosate Drugs 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000000454 electroless metal deposition Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- NZZAEWPIVSDHGF-UHFFFAOYSA-N 2-oxidodioxaphosphinan-2-ium Chemical compound [O-][O+]1OCCCP1 NZZAEWPIVSDHGF-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- LQGKDMHENBFVRC-UHFFFAOYSA-N 5-aminopentan-1-ol Chemical compound NCCCCCO LQGKDMHENBFVRC-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004440 Isodecyl alcohol Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- WPJWIROQQFWMMK-UHFFFAOYSA-L beryllium dihydroxide Chemical compound [Be+2].[OH-].[OH-] WPJWIROQQFWMMK-UHFFFAOYSA-L 0.000 description 1
- 229910001865 beryllium hydroxide Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- UURIHCKMZRIKSJ-UHFFFAOYSA-N dibutan-2-yl hydrogen phosphite Chemical compound CCC(C)OP(O)OC(C)CC UURIHCKMZRIKSJ-UHFFFAOYSA-N 0.000 description 1
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 description 1
- POWRQOUEUWZUNQ-UHFFFAOYSA-N didecyl phosphite Chemical compound CCCCCCCCCCOP([O-])OCCCCCCCCCC POWRQOUEUWZUNQ-UHFFFAOYSA-N 0.000 description 1
- QBCOASQOMILNBN-UHFFFAOYSA-N didodecoxy(oxo)phosphanium Chemical compound CCCCCCCCCCCCO[P+](=O)OCCCCCCCCCCCC QBCOASQOMILNBN-UHFFFAOYSA-N 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- YLFBFPXKTIQSSY-UHFFFAOYSA-N dimethoxy(oxo)phosphanium Chemical compound CO[P+](=O)OC YLFBFPXKTIQSSY-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- OYJSZRRJQJAOFK-UHFFFAOYSA-N palladium ruthenium Chemical compound [Ru].[Pd] OYJSZRRJQJAOFK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
A process for preparing N-hydroxyalkylaminomethylphosphonic acid or salts thereof which comprises contacting an alkanolamine, formaldehyde and a dialkyl phosphite in the presence of an alcohol under suitable reaction conditions to produce a reaction mixture, and hydrolyzing the reaction mixture under acidic or basic conditions. In one embodiment, the N-hydroxyalkylaminomethylphosphonic acid or salts thereof is catalytically oxidized to produce an N-phosphonomethylaminocarboxylic acid or salts thereof.
Description
<div class="application article clearfix" id="description">
<p class="printTableText" lang="en">New Zealand Paient Spedficaiion for Paient Number £87734 <br><br>
New Zealand No. International No. <br><br>
287734 <br><br>
PCT/US95/06799 <br><br>
TO BE ENTERED AFTER ACCEPTANCE AND PUBLICATION <br><br>
Priority dates: 01.07.1994;26.04.1995; <br><br>
Complete Specification Filed: 26.05.1995 <br><br>
Classification:(6) C07F9738 <br><br>
Publication date: 19 December 1997 <br><br>
Journal No.: 1423 <br><br>
NO DfOAKlK^QS <br><br>
NEW ZEALAND PATENTS ACT 1953 <br><br>
COMPLETE SPECIFICATION <br><br>
Title of Invention: <br><br>
Process for preparing IM-phosphonomethylamino carboxylic acids <br><br>
Name, address and nationality of applicant(s) as in international application form: <br><br>
MONSANTO COMPANY, a Delaware corporation of 800 North Lindbergh Boulevard, St Louis, MO 63167, United States of America <br><br>
WO 96/01266 <br><br>
-1- <br><br>
pct/ds95/06799 <br><br>
2877 <br><br>
PROCESS FOR PREPARING N-PHOSPHONOMETHYIAMINO CARBOXYLIC ACIDS <br><br>
10 BACKGROUND OF THE INVENTION <br><br>
This invention relates to a process for preparing n-hydroxyalkylaminomethylphosphonic acid or salts thereof. In one aspect, this invention relates to a new 15 and useful process for preparing N-hydroxyalkyl- <br><br>
aminomethylphosphonic acid or salts thereof from an alkanolamine, formaldehyde and a dialkyl phosphite. In another aspect, this invention relates to a process for preparing N-phosphonomethylaminocarboxylie acid or salts 20 thereof by the catalytic oxidation of <br><br>
N-hydroxyalkylaminomethylphosphonic acid or salts thereof. In yet another aspect, this invention relates to a process for preparing N-phosphonomethylglycine useful as a herbicide. 25 N-hydroxyalkylaminomethylphosphonic acid or salts thereof are useful as a raw material in the preparation of agricultural chemicals. <br><br>
N-phosphonomethylaminocarboxylic acids or salts thereof are useful as agricultural chemicals. Specifically, 30 N-phosphonomethylglycine, known also by its common name glyphosate, is a highly effective and commercially important phytotoxicant useful in controlling a large variety of weeds and crops. It is applied to the foliage of a very broad spectrum of perennial and annual 35 grasses and broad-leafed plants to achieve the desired control. Industrial uses include control of weeds along <br><br>
WO 96/01266 PCT/US95/06799 <br><br>
-2- <br><br>
roadsides, waterways, transmission lines, in storage areas, and in other nonagricultural areas. Usually glyphosate is formulated into herbicidal compositions in the form of its various salts which retain the anionic 5 form of glyphosate in solution, preferably in water. <br><br>
The reaction of a primary amine with an aldehyde and a phosphite diester is disclosed in Fields, NThe Synthesis of Esters of Substituted Amino Phosphonic Acids", J. Am. Chem. Soc., Vol. 74, pp. 1528-31 (1952). 10 However, the reaction product contains considerable amounts of the undesirable bis-phosphonomethylated product. Similarly, the reaction of a primary amine with formaldehyde and phosphorous acid is disclosed in Moedritzer and Irani, "'the Direct Synthesis of 15 a-Aminomethylphosphonic Acids. Mannich-Type Reactions with Orthophosphorous Acid", J. Org. Chem., Vol. 31, pp. 1603-1607 (1966). As in Fields, the reaction product is predominantly the bis-phosphonomethylated product. <br><br>
20 Barsukov et al, "Synthesis of New Complexons and <br><br>
Their Derivatives", Zhurnal Obshchei Khimii, <br><br>
Vol. 53, No. 6, pp. 1243-49 (1983) and Barsukov et al, "Synthesis of New Complexons of the Aliphatic Series and Investigation of the Mechanism of Acidic Dissociation", . 25 Zhurnal Obshchei Khimii, Vol. 55, No. 7, pp. 1594-1600 (1985) disclose the reaction of ethanolamine with paraformaldehyde and dimethyl hydrogen phosphite with a mole ratio of amine/phosphite of 1.0 and a mole ratio of formaldehyde/amine of 1.0. While these articles 30 disclose that the product is the mono- <br><br>
phosphonomethylated compound, reproduction of the reaction disclosed in the experimental section resulted in no mono-phosphonomethylated product being produced, i.e. 31P-NMR of the material analyzed in the Barsukov 35 example showed a 0% yield of <br><br>
N-(2-hydroxyethyl)aminomethylphosphonic acid <br><br>
07-21(12493)A <br><br>
287 73 4 <br><br>
-3- <br><br>
10 <br><br>
(See Example 3 herein). The process as described in the Barsukov et al articles is, therefore, incapable of preparing N-hydroxyalkylaminomethylphosphonic acid in a commercially practicable manner. <br><br>
A process for preparing N-hydroxyalkyl-aminomethylphosphonic acid or salts thereof which is economical, commercially viable, and can produce essentially only the mono-phosphonomethylated product is highly desirable. <br><br>
SUMMARY OF THE INVENTION <br><br>
It is an object of the invention to provide an efficient and economical process for preparing 15 N-hydroxyalkylaminomethylphosphonic acid or salts thereof that is commercially viable; and/or to provide a process for preparing N-hydroxyalkylaminomethylphosphonic acid or salts thereof for use in the production of 20 N-phosphonomethylaminocar boxy lie acid or salts thereof1, and/or to provide an efficient and economical process for preparing N-phosphonomethylaminocarboxylic acid or salts thereof for use as agricultural chemicals, and/or 25 to provide an efficient and economical process for preparing N-phosphonomethylglycine that is commercially viable; or at least to provide the public with a useful choice. <br><br>
According to the invention, a process for preparing N-hydroxyalkylaminomethylphosphonic acid or 30 salts thereof is provided which comprises contacting an alkanolamine, formaldehyde and a dialkyl phosphite in the presence of an alcohol under suitable reaction conditions to produce a reaction mixture, and hydrolyzing the reaction mixture under acidic or basic <br><br>
35 conditions. In one embodiment, the <br><br>
N-hydroxyalkylaminomethylphosphonic acid or salts <br><br>
N.Z. PAIL NT C <br><br>
8 OCT 199/ <br><br>
WO 96/01266 <br><br>
-4- <br><br>
PCT/US95/06799 <br><br>
thereof is catalytically oxidized to produce a N-phosphonomethylaminocarboxylic acid or salts thereof. <br><br>
Further according to the invention, a process for preparing N-phosphonomethylglycine or salts thereof is 5 provided which comprises contacting ethanolamine, <br><br>
formaldehyde and a dialkyl phosphite in the presence of an alcohol under suitable reaction conditions to produce a reaction mixture, hydrolyzing the reaction mixture under acidic or basic conditions to produce 10 N-hydroxyethylaminomethylphosphonic acid or salts thereof, and catalytically oxidizing the N-hydroxyethyl-aminomethylphosphonic acid or salts thereof. <br><br>
15 <br><br>
DETAILED DESCRIPTION OF THE INVENTION <br><br>
The invention relates to a process for preparing N-hydroxyalkylaminomethylphosphonic acid represented by the formula <br><br>
P <br><br>
H <br><br>
I <br><br>
HO ^ N—(-CH2")tt-OH <br><br>
20 or salts thereof comprising (a) contacting an alkanolamine represented by the formula H2N-fCH2-)-nOH <br><br>
wherein n is 2 to 6, formaldehyde and a dialkyl phosphite in the presence of 2m alcohol represented by the formula R(0H)m, wherein R is an alkyl group having 1 <br><br>
25 to about 18 carbon atoms and m is 1 to 3, under suitable conditions of time and temperature to produce a reaction mixture wherein the molar ratio of alkanolamine to phosphite is 1:1 to about 8:1 and the molar ratio of formaldehyde to alkanolamine is about 0.125:1 to about <br><br>
WO 96/01266 <br><br>
5- <br><br>
PCT/U S95/06799 <br><br>
3:1, and (b) hydrolyzing the reaction mixture under acidic or basic conditions. <br><br>
For producing N-phosphonomethylaminocarboxylic acid represented by the formula or salts thereof, the processes of the invention further comprise (c) catalytically oxidizing the N-hydroxyalkyl-aminomethylphosphonic acid or salts thereof. <br><br>
10 preparing N-phosphonomethylglycine or salts thereof comprising (a) contacting ethanolamine, formaldehyde and a dialkyl phosphite in the presence of an alcohol represented by the formula R(0H)m, wherein R is an alkyl group having l to about 18 carbon atoms and m is l to 3, 15 under suitable reaction conditions of time and temperature to produce a reaction mixture wherein the molar ratio of ethanoleunine to phosphite is about 1:1 to about 8:1 and the molar ratio of formaldehyde to alkanolamine is about 0.125:1 to about 3:1, (b) 20 hydrolyzing the reaction mixture under acidic or basic conditions to produce N-hydroxyethylaminomethyl-phosphonic acid or salts thereof, and (c) catalytically <br><br>
HO— <br><br>
5 <br><br>
The invention further relates to a process for <br><br>
WO 96/01266 PCT/U S9S/06799 <br><br>
-6- <br><br>
oxidizing the N-hydroxyethylaminomethylphosphonic acid or salts thereof. <br><br>
As used herein, the tern "salts of N-hydroxyalkylaminomethylphosphonic acid" means alkali 5 netal or alkaline earth netal salts of <br><br>
N-hydroxyalkylaminomethylphosphonic acid and the tern " salts of N-phosphonomethylaminocarboxylic acid" neans alkali metal or alkaline earth netal salts of N-phosphonomethylaminocarboxylie acid. Thus, the 10 products of the hydrolysis and oxidation reactions can include the acid, the salts thereof or any combination thereof, depending on the specific reaction and reaction conditions selected. <br><br>
Alkanolamines that can be employed according to 15 the invention are represented by the formula <br><br>
H2N eCH2)n— OH <br><br>
wherein n is 2 to 6. Examples of alkanolamines include ethanolamine, 3-amino-l-propanol, 4-amino-l-butanol, 20 5-amino-l-pentanol, 6-amino- 1-hexano 1 and mixtures thereof. The currently preferred alkanolamine is ethanolamine because of ready availability and the commercial significance of the product prepared using ethanolamine as the starting material. 25 Formaldehyde can be employed according to the invention as paraformaldehyde or as an aqueous solution of formaldehyde. Aqueous formaldehyde is commercially available as 37-50 weight percent aqueous solutions which may contain methanol, ethanol, or n-butanol. 30 Dialkyl phosphites, useful in the process of the invention, are commercially available or are readily prepared by conventional methods such as by reacting <br><br>
WO 96/01266 PCT/CS9S/06799 <br><br>
-7- <br><br>
PC13 or P4 with an alcohol including polyols. If a polyol is used as a react aunt, the phosphite product could have a cyclic structure, i.e. a cyclic phosphite ester. See, for example, Ford-Moore et al., Org. Syn., 5 Coll. Vol. XV, p. 955 and Cook et al., J. Chea. Soc., €35 (1949) for methods utilizing PC13 and U.S. Patent No. 2,661,364 for a method utilizing P4. The alkyl groups of the dialkyl phosphites are linear or branched alkyl groups having l to 18 carbon atoms and are 10 optionally substituted with -OH groups. The preferred alkyl groups cure those that jure branched or sterically hindered, or substituted with an -OH group. <br><br>
Examples of suitable dialkyl phosphites include, but are not limited to, diethyl phosphite, diisopropyl 15 phosphite, di(2-butyl) phosphite, dibutyl phosphite, dimethyl phosphite, didecyl phosphite, diisooctyl phosphite, dilauryl phosphite, di(1,2-dihydroxyethane)phosphite, di(l,2-dihydroxypropane)phosphite, 20 di(l,3-dihydroxypropane)phosphite, <br><br>
5,5-dimethyl-l, 3,2-dioxaphosphorinane-2-oxide, and mixtures thereof. The amount of alkanolamine utilized in the process of the invention cam be expressed as a molar ratio of alkanolamine starting material to 25 phosphite starting material. Broadly, the molar ratio of alkanolamine to phosphite is about 1:1 to about 8:1, preferably about 1:1 to about 3:1, and most preferably about 1:1 to about 1.5:1. <br><br>
The amount of formaldehyde utilized in the 30 process of the invention can be expressed as a molar ratio of formaldehyde starting material to alkanolamine starting material. Broadly, the molar ratio of formaldehyde to alkanolamine is about 0.125:1 to about 3:1, preferably about 0.66:1 to about 2.5:1, and most 35 preferably about 1.7:1 to about 2.3:1. <br><br>
WO 96/01266 <br><br>
-8- <br><br>
PCT/US95/06799 <br><br>
The reaction of alkanolamine, formaldehyde and phosphite is conducted at a suitable temperature which can vary over a wide range. The reaction temperature will generally be within the range of about 50°C to 5 about 150°C, preferably about 60*C to about 120°C and most preferably about 70*C to about 110eC. The reaction of alkanolamine, formaldehyde and phosphite is conducted for a suitable time which can vary over a wide range depending on various parameters, e.g. the reaction 10 temperature. Generally, the reaction time will be within the range of the time necessary for the phosphite to be consumed to about 16 hours, preferably about 2 hours to about 16 hours, and most preferably about 4 hours to about 6 hours. <br><br>
15 The reaction of alkanolamine, formaldehyde and phosphite is conducted in the presence of an alcohol solvent wherein the alcohol is represented by the formula R(0H)m and R is an alkyl group having 1 to about 18 carbon atoms and m is 1 to 3. The alkyl group, R, 20 can be linear or branched and preferably is the same alkyl group as that utilized in the dialkyl phosphite starting material. <br><br>
Examples of suitable alcohols include, but are not limited to, methanol, ethanol, isopropanol, 25 n-butanol, 2-butanol, isooctanol, decyl alcohol, <br><br>
isodecyl alcohol, lauryl alcohol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol, 2-hydroxymethyl-2-methyl-l,3-propanediol, l,3,5-trihydroxycyclohexane and mixtures thereof. 30 The hydrolysis reaction can be conducted under acidic or basic conditions using any one of several conventional methods known to those skilled in the art. <br><br>
When the hydrolysis reaction is conducted under 35 acidic conditions, a preferred method is to remove the excess alkanolamine from the reaction mixture together <br><br>
WO 96/01266 PCT/US9S/06799 <br><br>
—9- <br><br>
with any alcohol co-solvent optionally present followed by hydrolyzing the reaction mixture in hydrochloric acid. The concentration of the hydrochloric acid is preferably in the range of 6N HC1 to 12N HC1 5 (concentrated HC1). The temperature for the acid hydrolysis reaction is generally in the range of the boiling point of the EC1 to about 250*C, preferably 80°C to 120°C. Generally, the reaction tine will be within the range of the time necessary for hydrolysis to occur 10 to about 24 hours, preferably about 2 hours to about 16 hours. After the hydrolysis reaction is completed, the N-hydroxyalkylaminonethylphosphonic acid can be recovered by amy conventional method known to those skilled in the art. <br><br>
15 When the hydrolysis reaction is conducted under basic conditions, a preferred method is to contact the reaction mixture with an alkali netal hydroxide or alkaline earth netal hydroxide, preferably an alkali netal hydroxide. The concentration of the alkali netal 20 hydroxide or alkaline earth netal hydroxide is broadly within the range of about 15 weight percent to about 90 weight percent, preferably about 40 weight percent to about 60 weight percent, and nost preferably about 50 weight percent. The anount of alkali metal hydroxide 25 or alkaline earth netal hydroxide utilized in the hydrolysis reaction can be expressed as the ratio of equivalents of hydroxide to noles of phosphite starting material. Broadly, the ratio is about 2:1 to about 5:1, preferably about 2.5:1 to about 4:1, and most preferably 30 about 3:1. <br><br>
In the preferred embodiment of the hydrolysis conducted under basic conditions, the alcohol formed during the hydrolysis, i.e. the alcohol corresponding to the alkyl groups in the dialkyl phosphite, is removed 35 from the reaction mixture during hydrolysis, such as by distillation. For example, when diisopropyl phosphite <br><br>
WO 96/01266 PCT/US95/06799 <br><br>
is utilized in the process isopropyl alcohol is removed during the hydrolysis. <br><br>
The alkali metal hydroxides for use in the process of the invention include lithium hydroxide, <br><br>
5 sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide. Because of their ready availability and ease of handling, sodium hydroxide and potassium hydroxide are preferred, and sodium hydroxide is especially preferred. <br><br>
10 The alkaline earth metal hydroxides for use in the process of the invention include beryllium hydroxide, magnesium hydroxide, calcium hydroxide, <br><br>
strontium hydroxide and barium hydroxide. Calcium hydroxide is currently preferred because of its ready 15 availability. <br><br>
The temperature for the base hydrolysis reaction is generally in the range of about 80°C to about 250°c, preferably about 80°C to about 180°C, most preferably about 120°C to about 150°C. Generally, the reaction 20 time will be within the range of the time necessary for hydrolysis to occur to about 48 hours, preferably about 2 hours to about 24 hours and most preferably about 2 hours to about 16 hours. After the hydrolysis reaction is completed, the N-hydroxyalkylaminomethylphosphonic 25 acid or salts thereof can be recovered by any conventional method known to those skilled in the art. <br><br>
The oxidation of the N-hydroxyalkylaminomethyl-phosphonic acid or salts thereof is conducted in the presence of a catalyst. Suitable oxidation catalysts 30 are well known to those skilled in the art such as Raney copper and those described in U.S. 4,810,426 and U.S. 5,292,936, which are both incorporated by reference herein. <br><br>
In U.S. 4,810,426, the oxidation of 35 N-(2-hydroxyethyl)aminomethylphosphonic acid is conducted with an alkali metal hydroxide in the presence of water and a <br><br>
WO 96/01266 PCT/US95/06799 <br><br>
-11- <br><br>
suitable catalyst select from cadmium, zinc, copper, palladium and platinum and their respective oxides, hydroxides and salts. The oxidation reaction is conducted at a temperature of 200eC to 300°C. <br><br>
5 In U.S. 5,292,936, the oxidation of <br><br>
N- (2-hydroxyethyl) aminomethylphosphonic acid is conducted with an alkali metal hydroxide in the presence of em effective eunount of a Raney copper catalyst containing from about 50 peurts per million to about 10 10,000 parts per million of an element selected from the group consisting of chromium, titanium, niobium, <br><br>
tantalum, zirconium, vanadium, molybdenum, manganese, <br><br>
tungsten, cobalt, nickel and mixtures thereof. Of the above elements, chromium, molybdenum, and mixtures of 15 chromium and molybdenum are preferred. The oxidation reaction is conducted at a temperature between about 120#C and 220°C. <br><br>
Another particularly applicable type of oxidation catalysts are the supported mixed metal catalysts such 20 as those in U.S. Application Serial No. 08/269,722, and its subsequent continuation-in-part U.S. Application Serial No. 08/407,723, which are incorporated by reference herein. The supported mixed metal catalyst of the present invention is prepared by depositing from 25 about 1 wt.% to about 50 wt.%, based on the total weight of the catalyst, of an element selected from the group consisting of copper, cobalt, nickel, cadmium and mixtures thereof on a hydroxide resistant support having from about 0.05 wt.% to about 10 wt.% of an anchor metal 30 selected from the group consisting of platinum, <br><br>
palladium, ruthenium, silver, gold and mixtures thereof. <br><br>
Suitable hydroxide resistant supports include titanium oxide, zirconium oxide and carbon. Carbon is preferred. Activated carbon is even more preferred. 35 The particulate anchor metal deposited on the hydroxide resistant support can be a noble metal. By <br><br>
WO 96/01266 PCT/DS95/06799 <br><br>
-12- <br><br>
noble metal is meant gold, silver, platinum, palladium ruthenium or mixtures thereof. Platinum or palladium are preferred. Platinum is most preferred. The amount of anchor metal to be deposited on the hydroxide 5 resistant support can vary from about 0.05 wt.% to about 10 wt.%, based on the total weight of the catalyst. <br><br>
When less than about 0.05 wt.% anchor metal is deposited on the hydroxide resistant support, there is insufficient anchor metal to combine with the copper, 10 cobalt, nickel, and/or cadmium to provide a satisfactory catalyst. On the other hand, when more than about 10 wt.% anchor metal, based on the total weight of the catalyst, is deposited, on the support, the crystallite size of plated metal tends to increase. Larger crystal 15 sizes of the plated elemental metal sometimes leads to reduced catalytic performance. It is preferred to use from about 0.1 wt.% and about 5 wt.%, based on the total weight of the catalyst, of the anchor metal. The currently preferred supported mixed metal catalyst is a 20 carbon supported mixture of copper and platinum or palladium. <br><br>
Suitable hydroxide resistart supports containing a suitable anchor metal can be obtained commercially. <br><br>
The amount of deposited metal (i.e., copper, 25 cobalt, nickel and/or cadmium) should be sufficient to cover at least some of the embedded anchor metal particles. In addition to the coated particles the presence of at least some particles of the plating metal embedded on the support but not adherent on the anchor 30 metal can exist. X-ray Photoelectron Spectroscopy (XPS) is a technique which can be used to measure the relative concentration of surface atoms in the catalyst. Using this technique, it has been found that preferably in the catalysts of this invention the surface atomic ratio of 35 the deposited metal to the anchor metal is greater than 2.0, and more preferably, the XPS surface atomic ratio <br><br>
WO 96/01266 PCT/US95/06799 <br><br>
-13- <br><br>
is greater than the corresponding bulk atomic ratio. <br><br>
Any number of techniques can be used to deposit the anchor metal on the alkali resistant substrate and to deposit the copper, cobalt, nickel, and/or cadmium 5 onto the anchor metal. It is preferred, however, to use electroless metal deposition. Electroless metal deposition refers to the chemical deposition of an adherent metal coating on a suitable substrate in the absence of an externally applied electric source. 10 Regardless by the method of depositing the anchor metal onto the substrate, the size of the metal particles is a critical parameter in that it dictates the size of the crystals of copper, cobalt, nickel and cadmium to be deposited. The crystallite size of the 15 copper, cobalt, nickel, and cadmium should be less than about 500 Angstroms, and in the case of copper, it is preferred that the crystallite size is less than about 300 Angstroms. Although applicants do not wish to be bound by any particular theory, it is believed that a 20 uniform distribution of the anchor metal is best for achieving high reaction yields, but not necessary fast reaction rates. Further, it is believed that it is important to have small, well-reduced, highly-dispersed anchor metal particles. <br><br>
25 In practice, the substrate containing the anchor metal is added to and slurried in water. Next, a plating solution, e.g., copper plating solution, is prepared by mixing the plating solution in the appropriate proportions while the slurry of substrate 30 and water Ar- gently stirred at a temperature of about 0°c up to i0°C or higher in an open container. The plating solution containing a complexing agent and a reducing agent is added to the slurry in small increments by monitoring the pH with each addition. 35 After an appropriate time interval, the next increment of the slurry is slowly added. The amount of plating <br><br>
WO 96/01266 PCT/US95/06799 <br><br>
-14- <br><br>
solution added depends on the desired weight percent catalytic metal on the anchor metal in the catalyst. <br><br>
When the deposition of catalytic metal is completed, an essentially colorless filtrate results. <br><br>
5 Next, the finished catalyst is filtered and washed with distilled water. The filtration must be done in an inert atmosphere, such as a nitrogen atmosphere, to avoid exposure of the catalyst to air. Washing the catalyst removes unreacted components such 10 as parts per million impurities and unreacted reducing agent, such as formaldehyde. It has been found that from about 0.5 to 1.5 wt. % alkali metal is left on the catalyst, which is usually not harmful. The catalyst should be stored in a manner which avoids exposure to 15 oxygen, preferably by being kept under water. <br><br>
The currently preferred oxidation catalysts for use in the process of the invention are the catalysts of U.S. 5,292,936 and the supported mixed metal catalysts, with the supported mixed metal catalysts being 20 especially preferred. <br><br>
The reactions of the present invention can be conducted under atmospheric pressure or in a closed reaction vessel under a pressure. When the reactions are conducted in a pressure vessel, the pressure will 25 generally be the vapor pressure of the reaction mixture at the reaction conditions. <br><br>
30 General Procedures; Dialkyl phosphites were purchased from Aldrich Chemical when available. <br><br>
Phosphites which were not. commercially available were synthesized from PC13 and the corresponding alcohol by the method of Ford-Moore et. al Org. Syn. Coll. Vol. IV <br><br>
35 p. 955 or the method of Cook et. al. J. Chem. Soc. 635, (1949) . Formaldehyde was purchased from Aldrich <br><br>
WO 96/01266 PCT/US95/06799 <br><br>
-15- <br><br>
Chemical as a 37% solution in water. Paraformaldehyde (91-93%)was obtained from Hoechst Celanese Corporation. The yield of N-hydroxyalkylaminomethylphosphonic acids or their salts were determined by 31P-NMR in D20 using 5 methylenediphosphonic acid as an internal standard. Typically NMR samples were prepared in D20 containing conc. HC1 such that a sample pH»0.7 was obtained. NMR spectra were obtained on Varian VXR-300 or Varian VXR-4 00 spectrometers. Qualitative and quantitative mass 10 spectra were run on a Finnigan MAT90, a Finnigan 4500 and a VG40-250T spectrometers. <br><br>
Example 1 <br><br>
15 This comparative example illustrates the use of various dialkylphosphites in the synthesis of N-(2-hydroxyethyl)aminomethylphosphonic acid conducted without an alcohol being present. <br><br>
Diisopropylphosphite (17 g, 0.1 mmol), 20 paraformaldehyde (3.6 g, 0.12 mmol) and ethanolamine <br><br>
(48.8 g, 0.8 mmol) was charged into a round bottom flask equipped with magnetic stir bar and reflux condenser. The reaction was heated to 100°C for 16 h. Base hydrolysis of the intermediate esters was achieved by 25 adding 2 equiv. of NaOH (16 g of a 50% solution) and heating to 120°C for 16 hours. The reaction was allowed to cool and was concentrated under vacuum. Water (30 mL) was added to the reaction mixture and a sample was removed for 31P-NMR analysis. Yield of 30 N-(2-hydroxyethyl)aminomethylphosphonic acid (13%) was based on moles of phosphite charged. <br><br>
Summarized in Table l are the results of reactions run with a similar experimental protocol as described above but with different dialkylphosphites and various 35 ratios of reagents. <br><br>
WO 96/01266 PCT/US95/06799 <br><br>
-16- <br><br>
table 1 <br><br>
Preparation of N-2-Hydracye thyUininoroethytphcuphon ir Acid Using • Variety of Dialkylpbocphitet <br><br>
5 <br><br>
Jdafe <br><br>
Phosphite ffttumolaminc <br><br>
Formaldehyde* <br><br>
Reaction Temp *C <br><br>
Hydrolysis Method <br><br>
% Yield6 <br><br>
1C <br><br>
Dimethyl <br><br>
0.1 <br><br>
0.8 <br><br>
0.12 (p) <br><br>
80 <br><br>
base <br><br>
20 <br><br>
Diethyl <br><br>
0.1 <br><br>
0.8 <br><br>
0.1 <p) <br><br>
70 <br><br>
acid <br><br>
18s <br><br>
Diisopropyl <br><br>
15 <br><br>
0.1 <br><br>
Di-tec-butvl <br><br>
0.8 <br><br>
0.12 (p) <br><br>
100 <br><br>
base <br><br>
13 <br><br>
0.1 <br><br>
0.8 <br><br>
0.12 <j») <br><br>
100 <br><br>
base <br><br>
15 <br><br>
* Formaldehyde was charged as a 37% solution in water, (p) denotes when panfonnaldehyde was used. 20 b Yields determined by 31P-NMR and are based on moles of phosphite charged' Reactions were run for <br><br>
6 hours. <br><br>
Example 2 <br><br>
25 <br><br>
This example illustrates the advantage of using an alcohol as solvent in the preparation of N-(2-hydroxyethyl)aminomethylphosphonic acid from dialkylphosphites. <br><br>
30 A solution of paraformaldehyde (4.0 g, 0.13 mol), <br><br>
ethanolamine (6 mL, 0.097 mol), diisopropylphosphite (17 g, 0.1 mol) and 50 ml of isopropanol was stirred at 120°C for 16 hours. The solution was concentrated to dryneiss and 17 ml of 50% NaOH was added. The solution 35 was heated at reflux for 16 h, cooled to room temperature and concentrated under vacuum. Water (100 mL) was added to homogenize the mixture. The reaction was analyzed by 31P NMR in D20 at pH= 0.8. N- (2-Hydroxylethyl) aminomethylphosphonic acid was 40 obtained in 33% yield. <br><br>
WO 96/01266 PCT/US95/06799 <br><br>
-17-Bxample 3 <br><br>
This is a comparative example which illustrates the procedure reported by Barsukov et al, "Synthesis of New 5 complexons and Their Derivatives'*, Zhurnal Obshchei Khimii, Vol. 53, No. 6, pp 12243-49 (1983) for the preparation of N-(2-hydroxyethyl)aminomethylphosphonic acid utilizing dimethylphosphite. <br><br>
Dimethylphosphite (36g, 0.3227 mole) was added io dropwise over a period of l hour to a stirring solution of paraformaldehyde (9.8 g, 0.32 mole) and ethanolamine (20 g, 0.32 mole) below 20°C under nitrogen. The solution was heated to. 80°C for 1 hour and then cooled to room temperature. The solution was extracted with 15 350 ml of benzene as described in the paper. The benzene solution was then passed through a column containing 1 kg of alumina and the column was eluted with 1 liter of benzene. The benzene solution was concentrated under vacuum to dryness and 250 mL of Cone. 20 HC1 was added. The solution was heated to 110°C for 6 hours. Analysis of the reaction mixture by 31P-NMR showed o* yield of N-(2-hydroxyathyl)-aminomethylphosphonic acid. This Example demonstrates that contrary to what is disclosed in the Barsukov et al 25 reference, the process taught in the Barsukov et al reference produces no N-(2-hydroxyethyl)-aminomethylphosphonic acid. <br><br>
IBHfflPl* 4 <br><br>
30 <br><br>
This example illustrates the use of the Raney copper catalyst containing chromium of U.S. 5,292,936 to convert N-(2-hydroxyethyl)aminomethylphosphonic acid to N-phosphonomethylglycine. <br><br>
35 <br><br>
WO 96/01266 PCT/US95/06799 <br><br>
-18- <br><br>
Into a 160 ml nickel autoclave equipped with a stirrer is charged <br><br>
N-2-(hydroxyethyl)aminomethylphosphonic acid (16.84 g, o.n mol.) vater (11.3 al) and 45 weight % potassium 5 hydroxide (48.7 g, 0.39 mol.) and Raney copper catalyst containing 943 parts per million chromium (3.53 g). The autoclave is sealed and heated to 160°c. under a pressure of 9.5 Kg/cm2 while stirring the liquid phase in the autoclave. After 1.85 hours, hydrogen evolution 10 ceases. The yield of N-phosphonomethylglycine as its potassium salt is 98.5%. <br><br>
Example S <br><br>
15 This example illustrates the preparation of the supported mixed metal catalyst of the present invention. <br><br>
Into a one-liter glass beaker containing a teflon coated, 5 centimeter long, magnetic stirring bar, on a magnetic stirring plate are added distilled water 20 (169 ml) and wet 5% platinum on activated carbon in powder form, available from Degussa Corporation of Ridgefield Park, NY, which corresponds to 13.37 grams on a dry weight basis. In a separate one-liter beaker a copper plating solution is prepared by adding the 25 following components, most of which are available from MacDermid, Inc. of Waterbury, CT, with stirring in the following order: <br><br>
(1) 687 ml deionized water <br><br>
(2) 90 ml MACuPlex Ultra Dep 1000B* 30 (3) 54 ml MACuPlex Ultra Dep 1000A* <br><br>
(4) 18 ml MACuPlex Ultra Dep 1000D* <br><br>
(5) 5 ml 37% w/w formaldehyde <br><br>
35 <br><br>
* proprietary products of MacDermid TOTAL VOLUME 854 ml <br><br>
WO 96/01266 PCT/US95/06799 <br><br>
-19- <br><br>
According to MacDermid's product description for Product Code No. 17970, the resulting aqueous solution comprises the following active ingredients: <br><br>
5 Copper sulfate 4.0 g/1 <br><br>
Formaldehyde 6.0 g/1 <br><br>
Sodium hydroxide 9.0 g/1 <br><br>
Excess EDTA chelant 0.06 molar <br><br>
10 The resulting plating solution is filtered and then added to the slurry of the 5% platinum on activated carbon by adding 122 milliliter increments every 3 minutes at 40°C. The pH is monitored to verify the extent of the reaction. Time between additions is 15 extended when gas evolution becomes too vigorous. <br><br>
After the addition of the plating solution is completed, the catalyst is recovered by filtration using a 4 liter vacuum flask, a 350 ml coarse glass filter funnel, and a glass dome over the top of the funnel with 20 nitrogen. After filtration, the solid material is washed with three to four 250 milliliter portions of deionized water. The dry weight yield in this preparation is 18.4 grams. Microanalysis of the catalyst shows the elemental composition to be 13.4 wt.% 25 copper and 3.4 wt.% platinum, based on the total weight of the catalyst. The average copper crystal size as determined by XRD line broadening is found to be 157 Angstroms. <br><br>
30 <br><br>
This example shows another preparation of the supported mixed metal catalyst of the present invention. <br><br>
To a 2-liter glass beaker containing a Teflon polymer coated, 2.5 centimeter long, magnetic stirring <br><br>
35 bar on a magnetic stir plate is added distilled water (190 ml) followed by 5 wt.% platinum on activated <br><br>
WO 96/01266 PCT/US95/06799 <br><br>
-20- <br><br>
carbon, available from Degassa Corporation, <br><br>
corresponding to 16.42 grains (dry weight). An aqueous copper plating solution is prepared in a 4 liter beaker by adding the following components with stirring. <br><br>
5 <br><br>
(1) 500 ml DI water <br><br>
(2) NaKC4H406«4 H20 (tartrate) [29.99 g, 0.106 moles]; stir to dissolve <br><br>
(3) In a separate beaker, dissolve 11.79 gms of <br><br>
10 cuS04*5 H20 (3 gms Cuf) (0.047 mo.'es) in 400 ml deionized water <br><br>
(4) Add copper solution (3) to the resulting tartrate solution (2) <br><br>
(5) Add 13.60 grams of 50 wt% NaOH [0.17 mole] 15 (6) 11.35 ml 37 wt.% formaldehyde [0.15 mole] <br><br>
TOTAL VOLUME 1125 ml <br><br>
The resulting plating solution is added to the 20 slurry of 5 wt. % platinum on carbon in a total of about twelve, 79 ml increments with one increment every 2.5 minutes. The pH is monitored to verify the extent of the reaction and to delay incremental addition in time if and when the solution degassing becomes too vigorous. 25 The catalyst, after the plating solution is added to the slurry, is recovered by filtration as in Example 9. The dry weight yield is 20.03 grams. The composition is analyzed and is found to be 14.5% copper and 3.8% platinum, based on the total weight of the catalyst. 30 The average copper crystal dimension is 119 Angstroms. <br><br>
Example 7 <br><br>
This comparative example illustrates the 35 production of N-(2-hydroxyethyl)aminomethylphosphonic acid using diisopropylphosphite in the absence of <br><br>
WO 96/01266 PCT/US95/06799 <br><br>
-21- <br><br>
alcohol as solvent. <br><br>
A solution of 37% aqueous formaldehyde (8.2 g, 0.1 mole) and ethanolamine (9 g, 0.15 mole) was stirred at room temperature between one and two hours followed by 5 the addition of diisopropylphosphite (17 g, o.l mole). The reaction solution was heated at 80*C for 3 hours. Water (50 mL) and 16 mL of 50% NaOH was added to the reaction and the mixture was distilled in a Dean-Stark apparatus for 3 hours at 150°C to hydrolyze the 10 intermediate esters with the simultaneous removal of water, isopropanol and ethanolamine (80-100 mL total volume removed). A white precipitate formed which was dissolved with an additional 50 mL of water. Analysis of the reaction mixture by 31P-NMR showed a 49% yield of 15 N-(2-hydroxyethyl)aminomethylphosphonic acid and 6% <br><br>
yield of bis-N-(2-hydroxyethyl)aminomethylphosphonic acid. <br><br>
Example 8 <br><br>
20 <br><br>
This comparative example illustrates the production of N-(2-hydroxyethyl)aminomethylphosphonic acid when the amount of formaldehyde is varied and the reaction is conducted with a dialkyl phosphite in the absence of 25 alcohol as solvent. <br><br>
The reaction conditions employed are the same as those described in Example 7 except that the amount of formaldehyde used was varied between 1 and 2 equivalents based on phosphite. The results of these experiments 30 are summarized in Table 2. <br><br>
35 <br><br>
WO 96/01266 <br><br>
-22 <br><br>
PCT/US95/06799 <br><br>
TABLE 2 <br><br>
Prcpvmtioa of N-HydregyethyUminotneUiyiphotpltook: Add Using Diitopropyiphotphlle <br><br>
5 _ <br><br>
Mole % YleM <br><br>
Fhtxphhc Bthanolamfae FbrtMldehycJc1 Temp *C Mono* Bis*1 <br><br>
10 <br><br>
0.1 <br><br>
0.1 <br><br>
15 ai 0.1 0.1 <br><br>
20 <br><br>
* N-(2-hyiJroxyethyl)«rainomethylpho«phofik: add. bbU-N(-2-hydroxyethyl)amlriocnethy1pho«phonk add. <br><br>
BXftffPUt 9 <br><br>
25 <br><br>
This example illustrate the effect of varying the amount of formaldehyde employed in the reaction when a dialkyl phosphite is used in the presence of an alcohol solvent. <br><br>
30 In a typical reaction 37% formaldehyde (17 g, 0.2 <br><br>
mole) was added to a mixture of ethanolamine (6.1 g, 0.1 mole) in 100 mL of methanol. The mixture was heated to 70°C and dimethylphosphite (11 g, 0.1 mole) was added in one portion. The reaction was stirred at 70°C for <br><br>
35 several hours. Concentrated HC1 was added (50 mL) and the reaction was heated at 120 °C for 2 hours to hydrolyze the intermediate esters. Analysis of the reaction mixture by 31P-NMR showed a 74% yield of <br><br>
0.15 0.10 80 49 6 <br><br>
0.15 0.12 80 37 3 <br><br>
0.1S 0.16 80 47 6 <br><br>
0.15 0.18 80 48 10 <br><br>
0.15 020 80 38 11 <br><br></p>
</div>
Claims (28)
- l. A process for preparing N-hydroxyalkyl-aminomethylphosphonic acid represented by the formula 5 10 or salts thereof comprising: (a) contacting an alkanolamine represented by the formula wherein n is 2 to 6, formaldehyde and a dialkyl phosphite in the presence of an alcohol under suitable 20 conditions of time and temperature to produce a reaction mixture wherein the molar ratio of alkanolamine to phosphite is about 1:1 to about 8:1 and the molar ratio of formaldehyde to alkanolamine is about 0.125:1 to about 3:1, and 25 (b) hydrolyzing said reaction mixture under acidic or basic conditions.
- 2. The process of Claim 1 wherein said alcohol is represented by the formula R(0H)n wherein R is an alkyl group having 1 to about 18 carbon atoms and n is l to 3. 30
- 3. The process of Claim 1 wherein the molar ratio of formaldehyde to alkanolamine is about 0.66:1 to about 2.5:1.
- 4. The process of Claim 3 wherein the molar ratio of formaldehyde to alkanolamine is about 1.7:1 to about 35 2.3:1. 15 H2N (CH2 )n—OH
- 5. The process of Claim 1 wherein the molar ratio wo 96/01266 25 pct/cs95/06799 287734 of alkanolamine to phosphite is about 1:1 to about 3:1.
- 6. The process of Claim 1 wherein said phosphite is dimethyl phosphite.
- 7. The process of Claim 1 wherein the hydrolysis 5 is conducted under basic conditions.
- 8. The process of Claim 7 wherein said hydrolysis is conducted in the presence of an alkali metal hydroxide or alkaline earth metal hydroxide.
- 9. The process of Claim 7 wherein alcohol formed 10 during said hydrolysis is removed during said hydrolysis.
- 10. The process of Claim 1 wherein n is 2.
- 11. The process of Claim 1 further comprising: (c) catalytically oxidizing said 15 N-hydroxyalkyl-aminomethylphosphonic acid or salts thereof to produce an N-phosphonomethylaminocarboxylic acid represented by the formula 20 OH O 0 _ i II HO P^^N-tCH2lSTC— OH H<!> 25 or salts thereof. 30
- 12. The process of Claim 11 wherein the oxidation is conducted by contacting said N-hydroxyalkyl-aminomethylphosphonic acid or salts thereof with an alkali metal hydroxide in the presence of an effective eunount of a Raney copper catalyst containing from about 35 50 to about 10,000 parts per million of an element selected from the group consisting of chromium, 0 7- 21 ( 12-1 9 J ) A 287734 titanium, niobium, tantalum, zirconium, vanadium, molybdenum, manganese, tungsten, cobalt, nickel and mixtures thereof.
- 13. The process of Claim 11 wherein the oxidation 5 is conducted in the presence of an effective amount of a carbon supported mixed metal catalyst.
- 14. The process of Claim 13 wherein said catalyst is a carbon supported mixture of Cu and Pt or Pd.
- 15. The process of Claim 1 wherein said temperature • • 10 of the reaction of (a) is about 50 C to about 150 C.
- 16. A process for preparing N-phosphonomethylglycine or salts thereof comprising: (a) contacting ethanolamine, formaldehyde and a dialkyl phosphite in the presence of an alcohol under 15 suitable reaction conditions of time and temperature to produce a reaction mixture wherein the molar ratio of ethanolamine to phosphite is about 1:1 to about 8:1 and the molar ratio of formaldehyde to ethanolamine is about 0.125:1 to about 3:1, 20 (b) hydrolyzing said reaction mixture under acidic or basic conditions to produce N-hydroxyethyl-aminomethylphosphonic acid or salts thereof, and (c) catalytically oxidizing said N-hydroxyethyl-aminomethylphosphonic acid or salts thereof. 25
- 17. The process of Claim 16 wherein the oxidation is conducted by contacting said N-hydroxyalkyl-aminomethylphosphonic acid or salts thereof with an alkali metal hydroxide in the presence of an effective amount of a Raney copper catalyst containing from about 30 50 to about 10,000 parts per million of an element selected from the group consisting of chromium, titanium, niobium, tantalum, zirconium, vanadium, molybdenum, manganese, tungsten, cobalt, nickel and mixtures thereof. ^ 35
- 18. The process of Claim 16 wherein the oxidation - is conducted in the presence of an effective amount of a 07-21(12493)A -27- 287 73 k carbon supported mixed metal catalyst.
- 19. The process of Claim 16 wherein the hydrolysis is conducted under basic conditions.
- 20. The process of Claim 16 wherein the hydrolysis 5 is conducted in the presence of an alkali metal hydroxide or alkaline earth metal hydroxide.
- 21. The process of Claim 19 wherein alcohol formed during said hydrolysis is removed during said hydrolysis. 10
- 22. The process of Claim 16 wherein said alcohol is represented by the formula R(0H)m wherein R is an alkyl group having 1 to about 18 carbon atoms and m is 1 to 3.
- 23. The process of Claim 16 wherein the molar ratio 15 of ethanolamine to phosphite is about 1:1 to about 3:1.
- 24. The process of Claim 16 wherein the molar ratio of formaldehyde to ethanolamine is about 0.66:1 to about 2.5:1.
- 25. The process of Claim 24 wherein the molar ratio 20 of formaldehyde to ethanolamine is about 1.7:1 to about 2.3:1.
- 26. The process of Claim 16 wherein said phosphite is dimethyl phosphite.
- 27. A process for preparing N-hydroxyalkyl-aminomethyl-phosphonic acid of the formula defined in claim 1 or salts thereof substantially as herein described with reference to any example thereof.
- 28. A process for preparing N-phosphonomethylglycine or salts thereof substantially as herein described with reference to any example thereof. END OF CLAIMS N ~Z PATENT Q1 ' ■' ^ S 8 OCT tW i i R£0c(V t-t-/
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US26972294A | 1994-07-01 | 1994-07-01 | |
US42793695A | 1995-04-26 | 1995-04-26 | |
PCT/US1995/006799 WO1996001266A1 (en) | 1994-07-01 | 1995-05-26 | Process for preparing n-phosphonomethylamino carboxylic acids |
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EP (1) | EP0769014B1 (en) |
JP (1) | JPH10502370A (en) |
CN (2) | CN1061981C (en) |
AT (1) | ATE172465T1 (en) |
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BR (1) | BR9508166A (en) |
CA (1) | CA2193234A1 (en) |
DE (1) | DE69505534T2 (en) |
DK (1) | DK0769014T3 (en) |
ES (1) | ES2123989T3 (en) |
HU (1) | HU215465B (en) |
IL (1) | IL114411A (en) |
MX (1) | MX9700233A (en) |
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NZ (1) | NZ287734A (en) |
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CN1061980C (en) * | 1994-07-01 | 2001-02-14 | 孟山都公司 | Process for preparing N-phopshonomethylamino carboxylic acids |
US6232494B1 (en) * | 1998-02-12 | 2001-05-15 | Monsanto Company | Process for the preparation of N-(phosphonomethyl)glycine by oxidizing N-substituted N-(phosphonomethyl)glycine |
WO1999041260A1 (en) * | 1998-02-12 | 1999-08-19 | Monsanto Company | Process for making glyphosate by oxidizing n-substituted glyphosates |
US6417133B1 (en) | 1998-02-25 | 2002-07-09 | Monsanto Technology Llc | Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactions |
AU2003203448B2 (en) * | 1998-02-25 | 2006-05-18 | Monsanto Technology Llc | Deeply reduced oxidation catalyst and its use for catalyzing liquid phase oxidation reactions |
AR043078A1 (en) * | 1998-09-14 | 2005-07-20 | Dow Agrosciences Llc | PROCESSES TO PREPARE CARBOXYL ACIDS |
EP1283841B1 (en) | 2000-05-22 | 2005-11-16 | Monsanto Technology LLC | Reaction systems for making n-(phosphonomethyl)glycine compounds |
US7723375B2 (en) * | 2004-07-09 | 2010-05-25 | Arizona Board Of Regents, Acting On Behalf Of The University Of Arizona | Metabolites of wortmannin analogs and methods of using the same |
TW200624171A (en) * | 2004-09-15 | 2006-07-16 | Monsanto Technology Llc | Oxidation catalyst and its use for catalyzing liquid phase oxidation reactions |
TW200718706A (en) | 2005-04-25 | 2007-05-16 | Monsanto Technology Llc | Altering the crystal size distribution of N-(phosphonomethyl)iminodiacetic acid for improved filtration and product quality |
CN101085783B (en) * | 2007-07-04 | 2011-09-14 | 四川省乐山市福华通达农药科技有限公司 | Method for hydrolyzing glyphosate acid |
US8252953B2 (en) | 2008-05-01 | 2012-08-28 | Monsanto Technology Llc | Metal utilization in supported, metal-containing catalysts |
CN101717405B (en) * | 2009-11-16 | 2013-05-08 | 天津德凯化工股份有限公司 | Method for preparing phosphoric acid alkylamine ester |
CN114086398B (en) * | 2021-12-01 | 2022-07-26 | 常州畅韵工程材料有限公司 | Flame-retardant SBS (styrene butadiene styrene) modified asphalt waterproof coiled material and preparation method thereof |
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US2661364A (en) * | 1950-01-14 | 1953-12-01 | Du Pont | Preparation of organic phosphorus compounds, and in particular, of dialkyl phosphites |
US3567768A (en) * | 1964-04-24 | 1971-03-02 | Monsanto Co | Process for preparing amino alkylenephosphonic acids |
HU173170B (en) * | 1974-06-27 | 1979-03-28 | Chinoin Gyogyszer Es Vegyeszet | Process for producing n-phosphonomethyl-glycine |
US4442041A (en) * | 1982-06-30 | 1984-04-10 | Stauffer Chemical Company | Method for preparation of N-phosphonomethylglycine |
US4547324A (en) * | 1982-07-29 | 1985-10-15 | Stauffer Chemical Company | Method for preparation of N-phosphonomethylglycine |
US4439373A (en) * | 1982-12-27 | 1984-03-27 | Stauffer Chemical Company | Process for preparing phosphonomethylated amino acids |
US4810426A (en) * | 1986-01-28 | 1989-03-07 | Monsanto Company | Process for making glyphosate from n-phosphonomethyl-2-oxazolidone |
DE3721285A1 (en) * | 1987-06-27 | 1989-01-12 | Hoechst Ag | METHOD FOR PRODUCING N-PHOSPHONOMETHYLGLYCINE |
HU204533B (en) * | 1988-11-02 | 1992-01-28 | Nitrokemia Ipartelepek | Process for producing n-phosphono-methyl-glycine |
US4965403A (en) * | 1988-11-07 | 1990-10-23 | Monsanto Company | Oxidation/dealkylation process |
ATE111102T1 (en) * | 1989-06-15 | 1994-09-15 | Finchimica Srl | PROCESS FOR THE PRODUCTION OF N-PHOSPHONOMETHYLGLYCINE. |
US5292936A (en) * | 1993-04-12 | 1994-03-08 | Monsanto Company | Process to prepare amino carboxylic acid salts |
CN1061980C (en) * | 1994-07-01 | 2001-02-14 | 孟山都公司 | Process for preparing N-phopshonomethylamino carboxylic acids |
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CA2193234A1 (en) | 1996-01-18 |
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CN1161042A (en) | 1997-10-01 |
EP0769014A1 (en) | 1997-04-23 |
WO1996001266A1 (en) | 1996-01-18 |
HUT76816A (en) | 1997-11-28 |
MY112629A (en) | 2001-07-31 |
CN1061981C (en) | 2001-02-14 |
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US5602276A (en) | 1997-02-11 |
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